KR20080032164A - Flame retarded styrenic polymer foams and foam precursors - Google Patents

Abstract

Styrenic polymer foams, especially expanded and/or extruded styrenic polymer foams, are flame retarded by use of one or more flame retardant additives. These additives are i) a diether of tetrabromobisphenol-S, which ether groups do not contain bromine and wherein at least one of the ether groups is an allyl group; ii) a diether of tetrabromobisphenol-S, wherein at least one of the ether groups contains bromine; iii) a substituted benzene having a total of 6 substituents on the ring and wherein at least 3 of the substituents are bromine atoms and at least two of the substituents are C1-4 alkyl groups; iv) tribromoneopentyl alcohol; v) a tris(dibromoalkyl) benzenetricarboxylate in which each dibromoalkyl group contains, independently, 3 to 8 carbon atoms; vi) a brominated polybutadiene which is partially hydrogenated and/or aryl-terminated; vii) at least one brominated allyl ether of a novolac; viii) a brominated poly(l,3-cycloalkadiene); ix) a brominated poly(4-vinylphenol allyl ether); x) a brominated N,TSP-phenylenebismaleimide; xi) a brominated N, N'-(4,4'-methylenediphenyl)bismaleimide; xii) a brominated N,N'-ethylenebismaleimide; xiii) ethylenebis(dibromonorbornane-dicarboxrmide) ; xiv) tetrabromobisphenol-A; or xv) a combination of any two or more of i) through xiv).

Description

Flame Retardant Styrenic Polymer Foam and Foam Precursor {FLAME RETARDED STYRENIC POLYMER FOAMS AND FOAM PRECURSORS}

Styrenic polymer foams such as extruded polystyrene foam (XPS) and expandable polystyrene foam (EPS) are widely used. In many cases, it is desired to reduce the flammability of such products by mixing such products with flame retardants. It would therefore be desirable to provide flame retardants that can be used in the production of both types of products.

Flame-retardant extruded styrenic polymers, such as XPS, usually mix styrene-based polymers, flame retardants and foaming agents in an extruder, and then mix the resulting mixture with dies, such as varying thicknesses and widths, to provide the desired dimensions of the product It is made by extruding through boards. For use in such a process, it is important for the flame retardant to have good thermal stability and low corrosiveness to the metal to which the hot formulation will contact during the process. It is also desirable for the flame retardant to mix well with the other components in the extruder.

Flame retardant expandable styrenic polymers such as EPS are usually prepared by suspending polymerization of a mixture of styrene monomer (s) and flame retardant in water to form beads of styrene polymers. The small beads thus formed (eg, an average diameter of about 1 mm) are then pre-expanded with steam and then molded again with steam, which can be several meters in height, two to three meters in width, and cut into desired dimensions. Large foam blocks are produced. For use in this process, it is preferred that the flame retardant exhibit at least some solubility in the styrene-based monomer (s), especially styrene.

While some brominated flame retardants have been suggested or used for extruded styrenic polymers such as XPS and / or expandable styrene-based polymers such as EPS, high dose levels of flame retardants are typically required to achieve the desired effect. Due to the high cost of some flame retardants in addition to the high dose levels required for good effectiveness, there is a problem that a need for an effective solution arises.

The present invention provides novel flame retardant expanded and extruded styrenic polymers and methods of making them.

[Overview of invention]

The present invention provides styrenic polymer foams and styrene-based polymer foam precursors that are flame retardant by the use of one or more bromine-containing flame retardant additives detailed below.

Another embodiment of the present invention is a method for preparing the flame retardant styrenic polymer foam composition and the flame retardant styrenic polymer foam precursor composition.

One or more bromine containing flame retardant additives used in the preparation of the compositions of the present invention are as follows:

i) at least one dieter of tetrabromobisphenol-S, wherein the ether group does not contain bromine and at least one of the ether groups is an allyl group; or

ii) at least one dieter of tetrabromobisphenol-S, wherein at least one of the ether groups contains bromine; or

iii) a substituted benzene having a total of 6 substituents on the ring above, wherein not less than three of the substituents are bromine atoms, two of the substituents are one or more C _{1 -4} alkyl group; or

iv) tribromoneopentyl alcohol; or

v) at least one tris (dibromoalkyl) benzenetricarboxylate each dibromoalkyl group independently containing 3 to 8 carbon atoms; or

vi) at least one partially hydrogenated, aryl terminated, or partially hydrogenated and aryl terminated brominated polybutadiene; or

vii) at least one brominated allyl ether of novolak; or

viii) at least one brominated poly (1,3-cycloalkadiene); or

ix) at least one brominated poly (4-vinylphenol allyl ether); or

x) at least one brominated N, N'-phenylenebismaleimide; or

xi) at least one brominated N, N '-(4,4'-methylenediphenyl) bismaleimide; or

xii) at least one brominated N, N'-ethylenebismaleimide; or

xiii) ethylenebis (dibromonobonan-dicarboximide); or

xiv) tetrabromobisphenol-A; or

xv) a combination of any two or more of i) to xiv).

Of the above flame retardants, categories vii), viii), x), xi), and xii) are considered to be novel material compositions. At least some of the flame retardants of category vi) are also considered to be novel material compositions.

The bromine based flame retardant is characterized by a moderately high bromine content. In addition, experiences to date indicate that they exhibit good solubility in styrene-based monomers such as styrene, are easy to use to form EPS beads or granules, have a thermal stability suitable for use in styrene-based polymer foams, and preferred melt Having a temperature and appearing to be effective at low dose levels, they can be effectively used as flame retardants in EPS, XPS, or EPS and XPS type compositions. In addition, some but not all of the flame retardants appear to be adequately cost effective as flame retardants as they can be effectively used at low loading levels. In particular, flame retardant additives of categories i) to vi) are suitable for use in EPS and XPS type compositions. Flame retardant additives of category i) are more suitable for use in EPS type compositions, while flame retardant additives of categories vii) to xiii) are more suitable for use in XPS type compositions.

According to one embodiment of the present invention there is provided a flame retardant styrenic polymer foam composition comprising a styrenic polymer and a flame retardant amount of flame retardant and obtained by including the following in a foam recipe before or during foam formation:

i) at least one dieter of tetrabromobisphenol-S, wherein the ether group does not contain bromine and at least one of the ether groups is an allyl group; or

ii) at least one dieter of tetrabromobisphenol-S, wherein at least one of the ether groups contains bromine; or

iii) a substituted benzene having a total of 6 substituents on the ring above, wherein not less than three of the substituents are bromine atoms, two of the substituents are one or more C _{1 -4} alkyl group; or

iv) tribromoneopentyl alcohol; or

v) at least one tris (dibromoalkyl) benzenetricarboxylate each dibromoalkyl group independently containing 3 to 8 carbon atoms; or

vi) at least one partially hydrogenated, aryl terminated, or partially hydrogenated and aryl terminated brominated polybutadiene; or

vii) at least one brominated allyl ether of novolak; or

viii) at least one brominated poly (1,3-cycloalkadiene); or

ix) at least one brominated poly (4-vinylphenol allyl ether); or

x) at least one brominated N, N'-phenylenebismaleimide; or

xi) at least one brominated N, N '-(4,4'-methylenediphenyl) bismaleimide; or

xii) at least one brominated N, N'-ethylenebismaleimide; or

xiii) ethylenebis (dibromonobonan-dicarboximide); or

xiv) tetrabromobisphenol-A; or

xv) a combination of any two or more of i) to xiv).

In another embodiment of the present invention there is provided a flame retardant styrene-based polymer foam composition comprising a styrene-based polymer and a flame retardant in a flame retardant obtained by including the flame retardant in a foam recipe before or during the formation of the foam, wherein the styrene-based The polymeric foam composition may be in the form of a) expandable styrene-based polymer beads or granules, or b) in the form of extruded styrene-based polymer foams; When the styrene-based polymer foam composition is a), the flame retardant is as follows:

i) at least one dieter of tetrabromobisphenol-S, wherein the ether group does not contain bromine and at least one of the ether groups is an allyl group; or

ii) at least one dieter of tetrabromobisphenol-S, wherein at least one of the ether groups contains bromine; or

iii) a substituted benzene having a total of 6 substituents on the ring above, wherein not less than three of the substituents are bromine atoms, two of the substituents are one or more C _{1 -4} alkyl group; or

iv) tribromoneopentyl alcohol; or

v) at least one tris (dibromoalkyl) benzenetricarboxylate each dibromoalkyl group independently containing 3 to 8 carbon atoms; or

vi) at least one partially hydrogenated, aryl terminated, or partially hydrogenated and aryl terminated brominated polybutadiene; or

vii) at least one brominated allyl ether of novolak; or

A combination of any two or more of i) to vii) above;

When the styrene-based polymer foam composition is b), the flame retardant is as follows:

ii) at least one dieter of tetrabromobisphenol-S, wherein at least one of the ether groups contains bromine; or

iii) a substituted benzene having a total of 6 substituents on the ring above, wherein not less than three of the substituents are bromine atoms, two of the substituents are one or more C _{1 -4} alkyl group; or

iv) tribromoneopentyl alcohol; or

v) at least one tris (dibromoalkyl) benzenetricarboxylate each dibromoalkyl group independently containing 3 to 8 carbon atoms; or

vi) at least one partially hydrogenated, aryl terminated, or partially hydrogenated and aryl terminated brominated polybutadiene; or

vii) at least one brominated allyl ether of novolak; or

viii) at least one brominated poly (1,3-cycloalkadiene); or

ix) at least one brominated poly (4-vinylphenol allyl ether); or

x) at least one brominated N, N'-phenylenebismaleimide; or

xi) at least one brominated N, N '-(4,4'-methylenediphenyl) bismaleimide; or

xii) at least one brominated N, N'-ethylenebismaleimide; or

xiii) ethylenebis (dibromonobonan-dicarboximide); or

xiv) tetrabromobisphenol-A; or

A combination of any two or more of ii) to xiv) above.

In one embodiment of the invention, the flame retardant used to form the expandable styrene-based polymer is as follows:

i) at least one dieter of tetrabromobisphenol-S, wherein the ether group does not contain bromine and at least one of the ether groups is an allyl group; or

ii) at least one dieter of tetrabromobisphenol-S, wherein at least one of the ether groups contains bromine; or

iii) a substituted benzene having a total of 6 substituents on the ring above, wherein not less than three of the substituents are bromine atoms, two of the substituents are one or more C _{1 -4} alkyl group; or

iv) tribromoneopentyl alcohol; or

v) at least one tris (dibromoalkyl) benzenetricarboxylate each dibromoalkyl group independently containing 3 to 8 carbon atoms; or

vi) at least one partially hydrogenated, aryl terminated, or partially hydrogenated and aryl terminated brominated polybutadiene; or

vii) at least one brominated allyl ether of novolak; or

A combination of any two or more of i) to vii) above.

In this embodiment, no other flame retardants are used.

In another embodiment of the invention, the single flame retardant used to form the expandable styrene-based polymer is as follows: one or more synergists such as dicumyl, or one such as dibutyl tin maleate or hydrocalsite The above heat stabilizers are included in the expanded styrenic polymers:

i) at least one dieter of tetrabromobisphenol-S, wherein the ether group does not contain bromine and at least one of the ether groups is an allyl group; or

ii) at least one dieter of tetrabromobisphenol-S, wherein at least one of the ether groups contains bromine; or

iii) at least one substituted benzene having a total of six substituents on the ring, wherein at least three of the substituents are bromine atoms and at least two of the substituents are C _1-4 alkyl groups; or

iv) tribromoneopentyl alcohol; or

v) at least one tris (dibromoalkyl) benzenetricarboxylate each dibromoalkyl group independently containing 3 to 8 carbon atoms; or

vi) at least one partially hydrogenated, aryl terminated, or partially hydrogenated and aryl terminated brominated polybutadiene; or

vii) at least one brominated allyl ether of novolak; or

A combination of any two or more of i) to vii) above.

When such synergists are used, the amount is usually in the range of about 0.1 to about 0.4 weight percent based on the total weight of the polymer composition. When such a heat stabilizer is used, the amount is usually in the range of about 1 to about 5 weight percent based on the total weight of the polymer composition. It should be noted that the expanded styrenic polymer composition of the present invention may not include synergists, such as antimony oxide, used in non-expanded or unexpanded styrene based polymers.

In one embodiment of the invention, the flame retardant used to form the extruded styrenic polymer is as follows:

ii) at least one dieter of tetrabromobisphenol-S, wherein at least one of the ether groups contains bromine; or

iii) at least one substituted benzene having a total of six substituents on the ring, wherein at least three of the substituents are bromine atoms and at least two of the substituents are C _1-4 alkyl groups; or

iv) tribromoneopentyl alcohol; or

v) at least one tris (dibromoalkyl) benzenetricarboxylate each dibromoalkyl group independently containing 3 to 8 carbon atoms; or

vi) at least one partially hydrogenated, aryl terminated, or partially hydrogenated and aryl terminated brominated polybutadiene; or

vii) at least one brominated allyl ether of novolak; or

viii) at least one brominated poly (1,3-cycloalkadiene); or

ix) at least one brominated poly (4-vinylphenol allyl ether); or

x) at least one brominated N, N'-phenylenebismaleimide; or

xi) at least one brominated N, N '-(4,4'-methylenediphenyl) bismaleimide; or

xii) at least one brominated N, N'-ethylenebismaleimide; or

xiii) ethylenebis (dibromonobonan-dicarboximide); or

xiv) tetrabromobisphenol-A; or

A combination of any two or more of ii) to xiv) above.

In this embodiment, no other flame retardants are used.

In another embodiment of the invention, the single flame retardant used in the formation of the extruded styrenic polymer is as follows: one or more synergists such as dicumyl, or one such as dibutyl tin maleate or hydrocalsite The above heat stabilizers are included in the extruded styrenic polymers:

ii) at least one dieter of tetrabromobisphenol-S, wherein at least one of the ether groups contains bromine; or

iii) a substituted benzene having a total of 6 substituents on the ring above, wherein not less than three of the substituents are bromine atoms, two of the substituents are one or more C _{1 -4} alkyl group; or

iv) tribromoneopentyl alcohol; or

v) at least one tris (dibromoalkyl) benzenetricarboxylate each dibromoalkyl group independently containing 3 to 8 carbon atoms; or

vi) at least one partially hydrogenated, aryl terminated, or partially hydrogenated and aryl terminated brominated polybutadiene; or

vii) at least one brominated allyl ether of novolak; or

viii) at least one brominated poly (1,3-cycloalkadiene); or

ix) at least one brominated poly (4-vinylphenol allyl ether); or

x) at least one brominated N, N'-phenylenebismaleimide; or

xi) at least one brominated N, N '-(4,4'-methylenediphenyl) bismaleimide; or

xii) at least one brominated N, N'-ethylenebismaleimide; or

xiii) ethylenebis (dibromonobonan-dicarboximide); or

xiv) tetrabromobisphenol-A; or

A combination of any two or more of ii) to xiv) above.

When such synergists are used, the amount is usually in the range of about 0.1 to about 0.4 weight percent based on the total weight of the polymer composition. When such a heat stabilizer is used, the amount is usually in the range of about 1 to about 5 weight percent based on the total weight of the polymer composition. It should be noted that the extruded styrenic polymer composition of the present invention may not include synergists, such as antimony oxide, used in non-foamed or non-expandable styrenic polymers.

If a flame retardant is included in the foam recipe before or during foam formation, (a) the composition of the flame retardant in the foam obtained may not change, or (b) the foam obtained is in combination with one or more different materials from the flame retardant. The composition of the flame retardant may be partially changed or modified to contain some of the flame retardant and at least one of the different materials is preferably a flame retardant material different from the flame retardant, or (c) the foam obtained is with the flame retardant Other, the composition of the flame retardant may be completely changed to contain one or more materials from the flame retardant instead of any of the flame retardants and one or more of the different materials will be considered to be flame retardant. Thus, when the phrase "flame retardant obtained by inclusion in a foam recipe" (or phrase of similar meaning) is used herein, the word "flame retardant" may be obtained by including one or more constant flame retardants (if not used in the singular) in a foam recipe. The number of flame retardant materials is not limited in any way. Also as used herein, unless specifically noted otherwise, the term “flame retardant” or “flame retardant” does not limit the number of flame retardant components that may be present or used in the foam recipe or the foam obtained.

As used herein, the term “foam recipe” means any combination of materials that can be expanded to form a foam. Thus, a "foam recipe" can be, for example:

1) A mixture formed from a component comprising at least a styrenic polymer, at least one flame retardant of the invention, and at least one foaming agent, the mixture being extrudable to form an XPS foam; or

2) a mixture formed from a component comprising at least one styrenic monomer and at least one flame retardant of the invention, present in water or other liquid medium capable of carrying out suspension polymerization to form beads or granules of the styrenic polymer Mixture; or

3) Beads or granules prepared by suspension polymerization of the mixture as in 2), for example beads or granules which can be pre-expanded by steam to form large beads; or

4) Large pre-expanded beads or granules formed by pre-expanding beads or granules prepared by suspension polymerization of the mixture as in 2), for example with steam, wherein the large pre-expanded beads are molded, for example with steam. Thus large blocks of expandable styrenic polymers, such as EPS foam, can be produced.

In other words, "foam recipe" is any precursor mixture of the styrenic polymer foams of the present invention.

These and other embodiments and features of the invention will be more clearly described in the following detailed description.

Styrene series  polymer

The flame retardant styrenic polymer foams according to the invention are foamed (expandable) polymers of one or more polymerizable alkenyl aromatic compounds. At least one or more bulk (weight) of at least one alkenyl aromatic compound of formula is chemically bonded to form a styrenic homopolymer or copolymer:

[Wherein Ar is an aromatic hydrocarbyl group and R is a hydrogen atom or a methyl group].

Examples of such styrenic polymers include styrene, alpha-methylstyrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, ar-ethylstyrene, ar-vinylstyrene, ar-chlorostyrene, ar-bromostyrene ar-propylstyrene, ar-isopropylstyrene, 4-tert-butylstyrene, o-methyl-alpha-methylstyrene, m-methyl-alpha-methylstyrene, p-methyl-alpha-methylstyrene, ar-ethyl- Homopolymers of alpha-methylstyrene, and olefinic compounds capable of polymerizing two or more of the above-mentioned alkenyl aromatic compounds and other small amounts (weights) such as methyl methacrylate, acrylonitrile, maleic anhydride, citraconic anhydride, Itaconic anhydride, acrylic acid, copolymers with vinyl carbazole, and rubber-reinforced (natural or synthetic) styrenic polymers. Preferably at least 80% by weight of styrene is incorporated into the styrenic copolymer. Thus, in all embodiments of the invention presented herein, the styrenic polymer foam preferably comprises a styrenic copolymer wherein at least 80% by weight of the polystyrene or polymer is formed from styrene.

The styrenic polymer may be a linear polymer with substantially thermoplastics or a weakly cross-linked styrene-based polymer. Suitable procedures that can be used to prepare weak crosslinked styrenic polymers for use in foaming operations include, for example, US Pat. 4,448,933; 4,532,264; 4,604,426; 4,663,360 and 4,714,716.

Methods for producing styrenic foams, including XPS foams and EPS foams, are well known and reported in the literature. Thus, any suitable method can be used as long as the obtained foam is flame retardant by the use of one or more flame retardants according to the present invention in flame retardant amount. As a guideline for dose levels for use in foamed styrenic polymers, the LOI (limit oxygen index) of molded test specimens prepared from the non-foamable formulations is formulated by blending a small amount of flame retardant in the non-foamed crystalline styrenic polymers. It is preferable to measure. If the test specimen exhibits a LOI of at least one unit higher than a molded specimen of the same pure styrene-based polymer, its dose level will be suitable for use in the same foamed or foamable styrene-based polymer. The amount of flame retardant used in the styrenic foams of the present invention, including XPS foams and EPS foams, typically ranges from about 0.4 to about 6 weight percent, preferably from about 0.7 to about 5 weight percent, based on the total weight of the foam composition. . More preferably, the amount of flame retardant used in the styrenic foam ranges from about 1 to about 4 weight percent based on the total weight of the foam composition.

Extruded Switch Tiren Foam

Flame retardant styrenic polymer foams can be easily and quickly produced using known procedures. One useful general procedure, for example, involves thermoplasticizing the thermoplastic styrene-based polymer composition of the present invention in an extruder. Thermoplasticized resin is passed from the extruder to a mixer, such as a rotary mixer with a stud-type rotor, preferably having a stud-shaped inner surface engaged with the stud on the rotor. The thermoplastic resin and the volatile blowing or foaming agent are fed to the inlet end of the mixer and discharged from the outlet end, the flow of which is in the usual axial direction. The gel is passed from the mixer to the cooler and from the cooler to the die for extruding a conventional rectangular board. Such procedures are described, for example, in US Pat. 5,011,866. Other procedures include the use of systems that are extruded and foamed under subatmospheric, atmospheric and superatmospheric conditions. U.S. Patent No. As described in 5,011,866, one useful sub-air (vacuum) extrusion process is described in US Pat. No. 3,704,083. This process is described as having the advantage that the vacuum system of the type described in this document does not require a low permeability / high permeability foam mixture due to the effect of vacuum on the foaming process. Other disclosures relating to suitable foaming techniques are described, for example, in US Pat. 2,450,436; 2,669,751; 2,740,157; 2,769,804; 3,072,584; And 3,215,647.

expansion Possible Styrene series Bead  Or granule

The styrenic polymer composition of the present invention can be used to make expandable beads or granules with enhanced flame resistance. In general, the materials can be prepared using previously developed apparatus, process techniques and process conditions for such purposes, wherein the flame retardant compositions of the present invention have a substantially detrimental effect on the processing and overall properties of the styrenic polymers used. Because it does not have. In addition, well-established techniques for inflating expandable beads or granules and then forming or forming the expanded beads or granules into a desired product generally apply to expandable beads or granules formed from the styrenic polymer composition of the present invention. It is considered possible. Techniques suitable for the manufacture of expandable beads or granules are described, for example, in US Pat. 2,681,321; 2,744,291; 2,779,062; 2,787,809; 2,950,261; 3,013,894; 3,086,885; 3,501,426; 3,663,466; 3,673,126; 3,793,242; 3,973,884; 4,459,373; 4,563,481; 4,990,539; 5,100,923; And 5,124,365. The procedure for converting expandable beads of styrene-based polymers into foamed forms is described, for example, in US Pat. 3,674,387; 3,736,082; And 3,767,744.

Flame retardant

Flame retardants used in the practice of the invention are in the following categories:

i) at least one dieter of tetrabromobisphenol-S, wherein the ether group does not contain bromine and at least one of the ether groups is an allyl group; or

ii) at least one dieter of tetrabromobisphenol-S, wherein at least one of the ether groups contains bromine; or

iii) at least one substituted benzene having a total of six substituents on the ring, wherein at least three of the substituents are bromine atoms and at least two of the substituents are C _1-4 alkyl groups; or

iv) tribromoneopentyl alcohol; or

v) at least one tris (dibromoalkyl) benzenetricarboxylate each dibromoalkyl group independently containing 3 to 8 carbon atoms; or

vi) at least one partially hydrogenated, aryl terminated, or partially hydrogenated and aryl terminated brominated polybutadiene; or

vii) at least one brominated allyl ether of novolak; or

viii) at least one brominated poly (1,3-cycloalkadiene); or

ix) at least one brominated poly (4-vinylphenol allyl ether); or

x) at least one brominated N, N'-phenylenebismaleimide; or

xi) at least one brominated N, N '-(4,4'-methylenediphenyl) bismaleimide; or

xii) at least one brominated N, N'-ethylenebismaleimide; or

xiii) ethylenebis (dibromonobonan-dicarboximide); or

xiv) tetrabromobisphenol-A; or

Xv) a combination of any two or more of i) to xiv).

Flame retardants of categories i) and ii) are dieters of at least one tetrabromobisphenol-S. This compound can be represented by the formula:

In this case, in category i), R ¹ and R ² are the same or different and each has up to 10 carbon atoms, preferably up to 6 carbon atoms as alkyl, alkenyl, aryl, chloroalkyl, dichloroalkyl It contains; At least one of R ¹ and R ² is an allyl group.

Allyl propyl dieter of tetrabromobisphenol-S is an example of, but is not limited to, asymmetric ethers (R ¹ and R ² different from each other) within the flame retardant category. Particularly preferred diesters of tetrabromobisphenol-S in this category are bis (allyl ethers) of tetrabromobisphenol-S (3,5,3 ', 5'-tetrabromo-4,4'-dihydroxy Bis (allyl ether) of diphenyl sulfone).

In category ii), R ¹ and R ² are the same or different and at least one of R ¹ and R ² is 10 or less carbon atoms each, preferably bromoalkyl, dibromoalkyl, or tribromoalkyl, preferably It contains up to 6 carbon atoms. The 2,3-dibromopropyl 2,3-dichloropropyl diether of tetrabromobisphenol-S corresponds to an example of an asymmetric ether (R ¹ and R ² different from each other), but is not limited thereto. Preferred diesters of tetrabromobisphenol-S are symmetric ethers (ie, R ¹ and R ² are identical to each other). Some examples of such symmetric compounds include bis (2,3-dibromopropyl ether) (3,5,3 ', 5'-tetrabromo-4,4'-dihydroxy of tetrabromobisphenol-S Bis (2,3-dibromopropyl ether) of diphenyl sulfone), bis (2-bromopropyl ether) of tetrabromobisphenol-S, bis (3,4 of tetrabromobisphenol-S) Dibromobutyl ether), and other bromine-containing diesters of tetrabromobisphenol-S of the above formula. Particularly preferred flame retardants of category ii) include bis (2,3-dibromopropyl ether) of tetrabromobisphenol-S.

US patent No. See 4,777,297 and 4,006,118.

Category iii) flame retardant is at least one substituted benzene having a total of 6 substituents on and a bromine atom more than three substituents are two or more substituents of C _{1 -4} alkyl group, a ring. The ring position occupied by these six ring substituents may vary in any way. Compounds in this category include 1,2,3-tribromo-4,5,6-trimethylbenzene; 1,2,4-tribromo-3,5,6-trimethylbenzene; 1,3,5-tribromo-2,4,6-trimethylbenzene; 1,2,3,5-tetrabromo-4,6-dimethylbenzene; 1,2,4,5-tetrabromo-3,6-dimethylbenzene; 1,2,3,4-tetrabromo-5,6-dimethylbenzene; 1,2,3-tribromo-4,5,6-triethylbenzene; 1,2,4-tribromo-3,5,6-triethylbenzene; 1,3,5-brabromo-2,4,6-triethylbenzene; 1,2,3,5-tetrabromo-4,6-diethylbenzene; 1,2,4,5-tetrabromo-3,6-diethylbenzene; 1,2,3,4-tetrabromo-5,6-diethylbenzene; 1,2,3-tribromo-5-ethyl-4,6-dimethylbenzene; 1,3,5-tribromo-2,4-diethyl-6-methylbenzene; 1,3,5-tribromo-6-ethyl-2,4-dimethylbenzene; 1,2,4,5-tetrabromo-3-ethyl-6-methylbenzene; 1,3,5-tribromo-2,6-dimethyl-4-n-propylbenzene; 1,2,4,5-tetrabromo-3,6-di-tert-butylbenzene and the like (including other positional isomers), but are not limited thereto. The compound may be a suitable alkyl-substituted benzene (or mixture of alkyl-substituted benzenes) such as one xylene isomer or more than one mixture thereof, one trimethylbenzene isomer or more than one mixture thereof, It can be prepared using a Lewis acid-catalyzed bromination reaction of 1,3-diisopropylbenzene, and 1-methyl-2-n-butylbenzene. Ferric bromide is a suitable Lewis acid catalyst for the ring bromination reaction.

Flame retardant category iv) is tribromoneopentyl alcohol.

Flame retardants of category v) are at least one tris (dibromoalkyl) benzenetricarboxylate in which each dibromoalkyl group independently contains 3 to 8 carbon atoms. Three dibromoalkyl carboxylic acid ester groups may be present at 1,2,3-position, 1,2,4-position or 1,3,5-position. When the ester is a 1,2,3-isomer, it may also be referred to as an ester of hemimelitic acid; When the ester is 1,2,4-isomer, it may also be referred to as ester of trimellitic acid; If the ester is a 1,3,5-isomer, it may also be referred to as an ester of trimesic acid. Dibromoalkyl groups can also vary within themselves, in which case each dibromoalkyl group independently contains from 3 to about 8 carbon atoms, preferably from 3 to about 5 carbon atoms. Preferably the three dibromoalkyl groups each have the same carbon atom content in the range of 3 to about 8 carbon atoms, more preferably in the range of 3 to about 5 carbon atoms. Regardless of whether the dibromoalkyl groups all have the same carbon atom content or whether two or all three differ in the number of carbon atoms, one of the two bromine atoms is combined with the remaining bromine atoms on neighboring carbon atoms. It is preferably present on the furthest terminal carbon atom. Tris (2,3-dibromopropyl) 1,2,3-benzenetricarboxylate, tris (2,3-dibromopropyl) 1,2,4-benzenetricarboxylate, tris (2,3-dibromo Propyl) 1,3,5-benzenetricarboxylate, tris (3,4-dibromobutyl) 1,2,3-benzenetricarboxylate, tris (4,5-dibromopentyl) 1,2,4- Benzenetricarboxylate, tris (5,6-dibromohexyl) 1,3,5-benzenetricarboxylate, tris (6,7-dibromoheptyl) 1,2,4-benzenetricarboxylate, and tris ( 7,8-dibromooctyl) 1,3,5-benzenetricarboxylates fall under, but are not limited to, flame retardants of this category. Tris (2,3-dibromopropyl) 1,2,4-benzenetricarboxylate and tris (2,3-dibromopropyl) 1,3,5-benzenetricarboxylate are preferred members of this category of flame retardants. .

One process for preparing esters of flame retardants of category v) is to bromine tris (alkenyl) esters of benzenetricarboxylic acid under conventional bromination conditions used to add bromine to olefinic compounds using bromine as the brominating agent. In this regard, U.S. Pat. See 3,236,659.

Flame retardants of category vi) are at least one brominated polybutadiene which is partially hydrogenated, aryl terminated, or partially hydrogenated and aryl terminated. It is usually prepared by bromination of one or more oligomeric or polymeric polybutadienes partially hydrogenated and / or aryl terminated. As used herein, the term "polybutadiene" means a polymer made from 1,3-butadiene, which means that at least about 50 mole percent of the unsaturated portions in the polymer are 1,2- (vinyl) chains. . The polybutadiene preferably has at least about 70 mol% of unsaturated portions as 1,2-chains; More preferably, the polybutadiene has at least about 75 mole% of the unsaturated moieties as 1,2-chains. Particular preference is given to polybutadienes having, as 1,2-chain, unsaturated portions ranging from about 75 mol% to about 95 mol%. The polybutadiene may be atactic, isotactic, or syndiotactic. Brominated partially hydrogenated polybutadienes with or without aryl ends are preferred brominated polybutadienes. Terminal aryl groups, when present, typically have up to about 10 carbon atoms each and can be ring brominated; When an alkyl substituent is present on an aryl group, the alkyl group can be brominated. Both terminal brominated and brominated alkyl substituents may be present in the terminal aryl group. Preferably, the terminal aryl groups are phenyl or alkyl substituted phenyl groups each having up to about 10 carbon atoms. More preferred end groups are unsubstituted phenyl groups. When the polybutadiene is partially hydrogenated, the first polybutadiene oligomer or polymer (or mixture thereof) is usually hydrogenated such that about 10 to about 75 mole percent of the original unsaturated portion is saturated by hydrogen atoms. In other words, the unsaturated portion in the polybutadiene is usually maintained at a level of at least about 25 mole percent. Preferably, about 10 to about 60 mole percent of the original unsaturated portion is saturated with hydrogen. Preferred brominated polybutadienes in the practice of the present invention have at least about 75 mol% of 1,2-chains. Another preferred brominated polybutadiene of the present invention is aryl terminated and partially hydrogenated, in particular terminal aryl groups being unsubstituted phenyl groups. Brominated polybutadienes having both aryl end and partial hydrogenation are often referred to as brominated aryl terminated partially hydrogenated polybutadienes. Without wishing to be bound by theory, partial hydrogenation of polybutadiene is considered to improve the thermal stability and / or solubility of flame retardants within this category. Brominated partially hydrogenated polybutadienes, brominated aryl terminated polybutadienes, and brominated aryl terminated partially hydrogenated polybutadienes are considered novel material compositions.

One method of making flame retardants of category vi) is to bromine the appropriate polybutadiene. When the polybutadiene is partially hydrogenated, suitable polybutadiene polymers or oligomers usually and preferably have a number average molecular weight ranging from about 2,000 to about 200,000. More preferably, the number average molecular weight of the partially hydrogenated polybutadiene ranges from about 2,000 to about 20,000. When not partially hydrogenated, suitable polybutadiene polymers or oligomers usually and preferably have a number average molecular weight in the range from about 1,000 to about 20,000; If desired, polybutadiene polymers having a number average molecular weight of about 50,000 or less can also be used. More preferably, the number average molecular weight of the partially hydrogenated polybutadiene ranges from about 1,000 to about 10,000. The bromination reaction of the polybutadiene is carried out to at least saturate all residual aliphatic unsaturation of the oligomer (s) or polymer (s) with at least enough bromine or other brominating agents. In other words, preferably, essentially no aliphatic unsaturation remains in the final brominated product. In conventional production, polybutadiene, a solvent which is usually a halogenated hydrocarbon, and a polar protic solvent (which is at least part of the liquid medium) are disposed in the reaction zone, and then bromine is fed to the mixture in the reaction zone. do. Bromine can be supplied in any of several ways to sustain dilution in the reaction zone. Such methods are well known in the art and include using a turbulent flow mixer, feeding bromine to the surface, and dissolving bromine in a solvent before introducing it into the reaction zone. During the feeding of bromine, the mixture in the reaction zone is preferably maintained at a temperature in the range of about −10 ° C. to about 60 ° C. Before or after the bromine feed is initiated, some aqueous HBr is preferably added to the reaction mixture in the reaction zone, usually from about 1 to about 5 g of HBr per 50 g of polymer, preferably from about 2 to about 4 HBr per 50 g of polymer. Add in the range of g. Suitable solvents include dichloromethane, dibromomethane, bromochloromethane, trichloromethane, 1,2-dichloroethane, 1,2-dibromoethane, 1-bromo-2-chloroethane and the like. Mixtures of any two or more of them are included. Dichloromethane and bromochloromethane are the preferred solvents in the bromination reaction; Bromochloromethane is more preferred. Although not essential, the presence of HBr seems to help complete the reaction. Without wishing to be bound by theory, the presence of polar protic solvents such as water and / or alkanols is considered to minimize the addition of radical bromine. Examples of suitable polar protic solvents include water, methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 1-methyl-1-propanol, 2-methyl-1-propanol and tert-butanol and the like. Mixtures of two or more are included, but are not limited to these. As the polar protic solvent, a combination of water and ethanol is particularly preferable.

Flame retardant category vii) is at least one novolak brominated allyl ether. In this regard, according to conventional practice in the art, "novolak" refers to the reaction product between an acid catalyzed phenol and formaldehyde. Thus, brominated allyl ether of novolak is usually brominated allyl ether of phenol-formaldehyde novolak. The bromine content of novolak brominated allyl ether is usually at least about 49% by weight, preferably the bromine content is at least about 51% by weight. More preferred is a bromine content of at least about 53% by weight. Novolac brominated allyl ether is considered to be a novel substance composition.

One process for the manufacture of flame retardants of category vii) is to brominated allyl ethers of novolak under conventional bromination conditions used to add bromine to olefinic compounds using bromine as the brominating agent. Novorak's allyl ether is a US patent no. It can be prepared by reacting novolak and allylating agent in a procedure similar to that disclosed in 4,424,310. In preparing such brominated allyl ethers, novolaks generally have a weight average molecular weight of about 10,000 or less. In the preparation of novolak brominated allylic ether, the weight average molecular weight of novolak is preferably in the range of about 1,000 to about 5,000, more preferably in the range of about 1,100 to about 3,000.

Flame retardant category viii) is at least one brominated poly (1,3-cycloalkadiene). Brominated poly (1,3-cycloalkadienes) usually have at least one oligomeric or polymeric poly (1,3-cycloalkaca) having a number average molecular weight in the range from about 1,000 to about 10,000, preferably from about 1,500 to about 5,000. Diene) bromination reaction. Poly (1,3-cycloalkadienes) may be aryl terminated, partially hydrogenated, or aryl terminated and partially hydrogenated. Brominated partially hydrogenated poly (1,3-cycloalkadienes) with or without aryl ends are preferred brominated polybutadienes. Terminal aryl groups, if present, are usually phenyl or alkyl substituted phenyl groups, each having up to about 10 carbon atoms, preferably having up to about 10 carbon atoms, and can be ring brominated; When an alkyl substituent is present on the aryl group, the alkyl group may be brominated. Both terminal brominated and brominated alkyl substituents may be present in the terminal aryl group. Preferably, the terminal aryl groups are phenyl or alkyl substituted phenyl groups each having up to about 10 carbon atoms. More preferred end groups are unsubstituted phenyl groups. When the poly (1,3-cycloalkadiene) is partially hydrogenated, the first 1,3-cycloalkadiene oligomer or polymer (or mixture thereof) is usually from about 10 to about 55 to 65 mole percent of the original unsaturated moiety. Is hydrogenated to saturate with hydrogen atoms. As the ring size of the poly (1,3-cycloalkadiene) increases, the amount of unsaturation is required to increase; More specifically, the upper limit of saturation by hydrogen in poly (1,3-cyclohexadiene) is about 65 mol%, and the upper limit of saturation by hydrogen in poly (1,3-cycloheptadiene) is about 60 mol%, and the upper limit of saturation with hydrogen is about 55 mol% for poly (1,3-cyclooctadiene). In other words, the unsaturated portion in the poly (1,3-cycloalkadiene) is usually maintained at a level of about 35-45 mole percent or more, and the unsaturated portion preferably increases with larger 1,3-cycloalkadiene ring. Preferably, about 10 to about 40 mole percent of the original unsaturated portion is saturated with hydrogen. Poly (1,3-cyclopentadiene), poly (1,3-cyclohexadiene), poly (1,3-cycloheptadiene), poly (1,3-cyclooctadiene), etc. Several poly (1,3-cycloalkadienes), including aryl terminated and / or partially hydrogenated analogs, can be brominated to be used as flame retardants according to the present invention. Brominated poly (1,3-cyclohexadiene) is a preferred brominated poly (1,3-cycloalkadiene) in the practice of the present invention. More preferred brominated poly (1,3-cycloalkadienes) of the present invention are aryl terminated, in particular terminal aryl groups being unsubstituted phenyl groups. Brominated poly (1,3-cycloalkadienes) having aryl ends are often referred to as brominated aryl terminated poly (1,3-cycloalkadienes). Brominated poly (1,3-cycloalkadienes), in particular brominated aryl terminated poly (1,3-cycloalkadienes), are considered to be novel material compositions.

One method of making flame retardants of category viii) is to bromine poly (1,3-cycloalkadienes). The bromination reaction is carried out to at least saturate all residual aliphatic unsaturation in the oligomer (s) or polymer (s) with at least enough bromine or other brominating agents. In other words, there is essentially no aliphatic unsaturation left in the final brominated product. The preparation of brominated poly (1,3-cycloalkadiene) from poly (1,3-cycloalkadiene) is similar to the preparation of brominated polybutadiene as described above.

Flame retardants of category ix) are at least one brominated poly (4-vinylphenol allyl ether), wherein "at least one" means that the amount of bromine in the molecule is different. As is known in the art, it can be prepared by reacting brominated poly (4-vinylphenol) with an allylating agent; In this regard, US Patent No. See 4,424,310. Brominated poly (4-vinylphenol allyl ether) generally has a number average molecular weight in the range of about 3,000 to about 20,000, preferably in the range of about 5,000 to about 10,000. The bromine content of brominated poly (4-vinylphenol allyl ether) oligomers or polymers is usually at least about 40% by weight, preferably the bromine content is about 45% by weight. More preferred is a bromine content of at least about 48% by weight.

Flame retardants of category x) are at least one brominated N, N'-phenylenebismaleimide, wherein "at least one" means that the amount of bromine in the molecule is different. The brominated N, N'-phenylenebismaleimide may be the 1,3- or 1,4-phenylene isomer; Preference is given to 1,3-phenylene isomers. There are preferably about 3 to about 4 bromine atoms in the brominated N, N'-phenylenebismaleimide molecule. More preferably, there are about four bromine atoms in the molecule. Thus particularly preferred brominated N, N'-phenylenebismaleimide is tetrabromo-N, N'-1,3-phenylenebismaleimide.

One method of preparing flame retardants of category x) is to bromine N, N'-phenylenebismaleimide. The bromination reaction of N, N'-phenylenebismaleimide is carried out using at least enough bromine or other brominating agents such that a bromine atom is placed at each of the four available imido ring positions. In conventional production, N, N'-phenylenebismaleimide, a solvent, usually a halogenated hydrocarbon, is placed in the reaction zone and then bromine is fed to the mixture in the reaction zone. During bromine supply, the mixture in the reaction zone is preferably maintained at a temperature in the range from about 40 ° C to about 60 ° C. Suitable solvents include dichloromethane, dibromomethane, bromochloromethane, trichloromethane, 1,2-dichloroethane, 1,2-dibromoethane, 1-bromo-2-chloroethane and the like. Mixtures of any two or more are included. Dichloromethane is a preferred solvent for the bromination reaction. The bromination conditions of N, N'-phenylenebismaleimide are not optimized.

Flame retardant category xi) is at least one brominated N, N '-(4,4'-methylenediphenyl) -bismaleimide, wherein "at least one" means that the amount of bromine in the molecule is different. Preferably, about 3 to about 4 bromine atoms are present in the brominated N, N-phenylenebismaleimide molecule. More preferred are brominated N, N '-(4,4'-methylenediphenyl) bismaleimide molecules having about 4 bromine atoms. Particularly preferred brominated N, N '-(4,4'-methylenediphenyl) bismaleimide is tetrabromo-N, N'-(4,4'-methylenediphenyl) bismaleimide.

One method of making flame retardants of category xi) is to bromine N, N '-(4,4'-methylenediphenyl) -bismaleimide. The bromination reaction is carried out using at least sufficient bromine or other brominating agents such that bromine atoms are placed at each of the four available imido ring positions. Preparation of brominated N, N '-(4,4'-methylenediphenyl) -bismaleimide, except that the mixture in the reaction zone is preferably maintained at a temperature in the range of about 25 ° C to about 45 ° C during bromine feeding. Is similar to the preparation of brominated N, N'-phenylenebismaleimide as described above.

Flame retardant category xii) is at least one brominated N, N'-ethylenebismaleimide, wherein "at least one" means that the amount of bromine in the molecule is different. There are preferably about 3 to about 4 bromine atoms in the brominated N, N'-ethylenebismaleimide molecule. Preferably, there are about 4 bromine atoms in the molecule. Particularly preferred brominated N, N'-ethylenebismaleimide is tetrabromo-N, N'-1,3-ethylenebismaleimide.

One method of preparing flame retardants of category xii) is to bromine N, N'-ethylenebismaleimide. The bromination reaction is carried out using at least sufficient bromine or other brominating agents such that bromine atoms are placed at each of the four available imido ring positions.

The preparation of brominated N, N'-ethylenebismaleimide is carried out with bromination N as described above, except that the mixture in the reaction zone is preferably maintained at a temperature in the range of about 25 ° C to about 45 ° C. Similar to the preparation of N'-phenylenebismaleimide.

Flame retardant category xiii) is ethylenebis (Dibiromonobonan-dicarboximide).

Flame retardant category xiv) is tetrabromobisphenol-A.

blowing agent

Any of a wide variety of known blowing or foaming agents can be used to make the expanded or foamed flame retardant polymers of the present invention. U.S. Patent No. 3,960,792 provides a list of some suitable substances. In general, volatile carbon-containing chemicals are most widely used for this purpose. These include, for example, aliphatic hydrocarbons including ethane, ethylene, propane, propylene, butane, butylene, isobutane, pentane, neopentane, isopentane, hexane, heptane and mixtures thereof; Volatile halocarbons and / or halohydrocarbons such as methyl chloride, chlorofluoromethane, bromochlorodifluoromethane, 1,1,1-trifluoroethane, 1,1,1,2-tetrafluoroethane, Dichlorofluoromethane, dichlorodifluoromethane, chlorotrifluoromethane, trichlorofluoromethane, sym-tetrachlorodifluoroethane, 1,2,2-trichloro-1,1,2-tri Fluoroethane, sym-dichlorotetrafluoroethane; Volatile tetraalkylsilanes such as tetramethylsilane, ethyltrimethylsilane, isopropyltrimethylsilane and n-propyltrimethylsilane; And mixtures of such materials. One preferred fluorine-containing foaming agent is 1,1-difluoroethane, also known as HFC-152a (FORMACEL Z-2, EI duPont de Nemours and Co.), based on its reported desirable ecological properties. . Watery plant materials such as finely divided corn cobs can also be used as foaming agents. U.S. Patent No. As described in 4,559,367, such vegetable materials also serve as fillers. Particular preference is given to using carbon dioxide as a blowing agent or at least as a component of the blowing agent, which is based on its harmlessness to the environment and its low cost. Processes using carbon dioxide as a foaming agent are described, for example, in US Patent No. 5,006,566, Preferred Foaming Agents are U.S. Pat. 5,189,071 and 5,189,072, and the preferred foaming agents include a combination of water and carbon dioxide. 5,380,767. Other preferred foaming agents and foaming agent mixtures include nitrogen or argon in the presence or absence of carbon dioxide. If desired, such foams or foam mixtures may be mixed with alcohols, hydrocarbons or ethers of appropriate volatility. For example, U.S. Patent No. See 6,420,442.

Other ingredients

Extrusion aids (such as barium stearate or calcium stearate), peroxides or CC synergists, acid removers (such as magnesium oxide or tetrasodium pyrophosphate), dyes, pigments, fillers, stabilizers, antioxidants, antistatic agents, Components such as reinforcing agents and the like can be included in the foam compositions of the present invention. If desired, nucleating agents that control cell size (eg, talc, calcium silicate or indigo) can be included in the styrene-based polymer compositions used to prepare the flame retardant expanded or expanded styrene-based polymers of the present invention. Each particular auxiliary material selected for use in the foam composition of the present invention is used in conventional amounts, and they should be selected so as not to substantially adversely affect the properties of the final polymer foam composition for their desired utility.

As mentioned above, in some preferred embodiments of the present invention, no other flame retardant is used. In another preferred embodiment of the invention, one or more synergists such as dicumyl, or one or more heat stabilizers such as dibutyl tin maleate or hydrocalcite are included in the styrenic polymer foam composition. When such synergists are used, the amount is usually in the range of about 0.1 to about 0.4 weight percent based on the total weight of the polymer composition. When such a heat stabilizer is used, the amount is usually in the range of about 1 to about 5 weight percent based on the total weight of the polymer composition. It should be noted that the expanded styrene-based polymer composition of the present invention and the extruded styrene-based polymer composition of the present invention may both contain no synergist used for non-foamed or unexpanded styrene-based polymers such as antimony oxide. something to do.

The following examples are presented for purposes of illustration and are not intended to limit the scope of the invention.

Example  1-23 and Comparative example CA

To illustrate the flame retardant effect, a polystyrene composition was prepared to perform ASTM Standard Test Method D 2863-87, commonly referred to as Limit Oxygen Index (LOI) test. In this test, the higher the LOI value, the greater the flame resistance of the composition. Test specimens were prepared using Styron ^® 678E polystyrene (Dow Chemical Company). This material is a general purpose nonflammable degree of unreinforced crystalline polystyrene (GPPS). Its melt flow index is 10 g / 10 min at 200 ° C. and 5 kg pressure with a LOI of 18.0. Table 1 sets forth the chemical nature of the flame retardants used in Examples 1-23 and the scope of the invention to which such flame retardants fall. Table 1 also shows the loadings, bromine content, and LOI results of Examples 1-23. Each flame retardant was used without any other flame retardant or flame retardant aid or synergist. In Comparative CA, test specimens were prepared from the same polystyrene without mixing with any flame retardants or additives.

To form the test specimens of Examples 1-23, the following general procedure was used: Using a Haake rheomix 600 machine, a known amount, such as 45 g of GPPS, was placed in a mixing chamber heated at 15O < 0 > C and about 2 Mix at 100 rpm for minutes. A measurable amount of flame retardant to be evaluated was then added to the melted GPPS and mixing was continued for about 3 minutes. The rotor was then stopped and the mixing chamber opened to collect the resulting compound blend and then cooled to room temperature. Three batches were prepared in this manner for each flame retardant to obtain sufficient material for compression molding test plaques.

Prior to compression molding, each batch was first powdered and passed through a 4 mm sieve. About 115 g of the powder was then poured into a 190 x 190 mm insert at room temperature. Inserts containing powder were placed at about 20 kN for 1 minute between platens heated at 180 ° C. A pressure of 200 kN was then applied for an additional about 7 minutes. The insert was then cooled between two other platens at 20 ° C. at a pressure of 200 kN for about 8 minutes. Then 190 x 190 x 2.75 (+/- 0.15) mm plaque was removed from the mold. Two large plaques of 95 × 95 mm and 17 bars of 10 × 95 mm were cut from the large plaques. The bars were used for LOI evaluation.

Table 1

Example  24 ~ 27

The same procedure as in Examples 1-23 was carried out using the flame retardant of the invention in combination with another component useful for the preparation of flame retardant styrenic polymer compositions. Polystyrene used the same kind as used in Examples 1-23 and CA. The remaining components used were dicumyl (flame retardant synergist), dibutyl tin maleate (heat stabilizer), and hydrotalcite (heat stabilizer). Hydrotalcite was used as DHT-4A (Kyowa Chemical Company). Dicumyl is the common name for 2,3-dimethyl-2,3-diphenylbutane. The composition of the test compositions and the test results are summarized in Table 2.

TABLE 2

Example  28-33 and Comparative example CB

Expandable polystyrene beads (EPS) were prepared with and without addition of the flame retardant of the present invention. In the procedure for flame retardant EPS beads, 0.28 g of polyvinyl alcohol (PVA) was dissolved in 200 g of deionized water and then poured into a 1-liter glass container. Separately, a solution was formed from 0.64 g of dibenzoyl peroxide (75% in water), 0.22 g of dicumyl peroxide, and 1.45 g of the flame retardant of the present invention in 200 g of styrene. This latter solution was poured into the vessel containing the PVA solution. The obtained liquid was charged to a polymerization reactor and mixed at 100 rpm in the presence of a baffle using a propeller type stirrer to generate shear stress in the reactor. The following heating profiles were then performed on the mixture:

From 20 ° C. to 90 ° C. within 45 minutes, then maintained at 90 ° C. for 4.25 hours (first stage operation);

From 90 ° C. to 13 ° C. within 1 hour and then held at 13 ° C. for 2 hours (second step operation); And

From 130 ° C to 20 ° C within 1 hour.

At the end of the first step, the reactor was pressurized with nitrogen (2 bar). Upon cooling, the reactor was emptied and the mixture filtered. The flame retardant beads formed in the process were dried overnight at 60 ° C. and then sieved to determine the bead size distribution. Comparative Example CB was carried out in the same manner except that no flame retardant additive was used.

The flame retardants tested and the categories to which they belong are:

i) bis (allyl ether) (FR-1) of tetrabromobisphenol-S;

ii) bis (2,3-dibromopropyl ether) of tetrabromobisphenol-S (FR-2);

iii) tetrabromoxylene (FR-3);

iv) tribromoneopentyl alcohol (FR-4);

v) tris (dibromopropyl) 1,2,4-benzenetricarboxylate (FR-5);

vi) brominated phenyl terminated partially hydrogenated polybutadiene (FR-6).

For convenience, these specific flame retardants are listed in Table 3 according to the category to which they belong. Thus, Table 3 shows the composition and summarizes the results for that group of examples.

TABLE 3

Example  34-37

Examples 34-37 are tris (dibromoalkyl) benzenetricarboxylate, each brominated aryl-terminated partially hydrogenated polybutadiene, and brominated 1,2-, each dibromoalkyl group containing independently 3 to 8 carbon atoms. To illustrate the synthesis of flame retardants of polybutadiene, ie categories v) and vi).

Example  34

Triallyl 1,2,4-benzenetricarboxylate (201 g, 0.609 mol) was added to dichloromethane (˜1 kg) in a flask in a circulation bath. Bromine (292 g, 1.83 mol) was added dropwise over 30 minutes to the triallyl benzenetricarboxylate solution under stirring. The circulation bath temperature was 3 to 6 ° C. and the reaction temperature during bromine addition was in the range of 15 to 25 ° C. After the bromine addition was complete, the reaction mixture was heated to 35 ° C. for 30 minutes under stirring. Aqueous sodium sulfite was added to the reaction mixture to remove excess bromine, and then the reaction mixture was neutralized by addition of aqueous sodium carbonate (10 wt%; at pH-10-12). Once two layers were formed, the dichloromethane layer was separated from the aqueous layer. The solvent was removed in vacuo from the separated dichloromethane layer. Product Tris (2,3-dibromopropyl) 1,2,4-benzenetricarboxylate was a clear viscous liquid containing 59.2 wt.% Bromine.

Example  35

Triallyl 1,3,5-benzenetricarboxylate (5 g, 0.015 mol) was added to dichloromethane (-25 g) in a flask in a circulation bath. Bromine (7.3 g, 0.045 mol) was added dropwise to the triallyl benzenetricarboxylate solution under stirring. The circulation bath temperature was 3-6 ° C. and the reaction temperature during bromine addition was in the range of 10-25 ° C. After the bromine addition was complete, the reaction was heated to 35 ° C. for 30 minutes under stirring. Aqueous sodium sulfite was added to the reaction mixture to remove excess bromine, and then the reaction mixture was neutralized by addition of aqueous sodium carbonate (10 wt%; at pH-10-12). Once two layers were formed, the dichloromethane layer was separated from the aqueous layer. The solvent was removed in vacuo from the separated dichloromethane layer. Product Tris (2,3-dibromopropyl) 1,3,5-benzenetricarboxylate was a clear viscous liquid. After several months, the product was partially solidified.

Example 36

Phenyl terminated partially hydrogenated polybutadiene (35 g; 0.388 mol of unsaturated butylene units, density = 0.930; 60 wt% of unsaturated portion: 45 wt% vinyl, 10 wt% trans-1,4, cis-1,4 5 %, 0.250 mol saturated butyl unit and phenyl unit -0.019 mol; M _n -1,800, Aldrich Chemical Company) were added to dichloromethane (1 kg) and methanol (115 g) in a flask in a circulation bath. In the steam addition of bromine, the circulation bath temperature was set to 20 ° C. Bromine was placed in a separate flask equipped with a gas sparger and heated to 58-60 ° C. While stirring the polybutadiene mixture, bromine was fed to the polybutadiene mixture by a sparger containing nitrogen as the carrier gas. One hour after starting the bromine feed, 1 mL of aqueous HBr (48 wt.%) Was added to the reaction flask and the reaction temperature was raised to 30 ° C. After a total of 1.5 hours of feed time, an additional 2 mL of aqueous HBr (48 wt.%) Was added. After a total of 3 hours of feed time, an additional 2 mL of HBr (aq., 48 wt.%) Was added and the reaction temperature was raised to 33 ° C. After a total of 4 hours bromine feed time, bromine feed was stopped. The bromination reaction process was monitored by ¹ H NMR (relative to the unsaturated group). Aqueous sodium sulfite was added to the reaction mixture to remove the bromination reaction. Aqueous sodium carbonate was then added to the reaction mixture to neutralize the aqueous solution (to pH-9). Once two layers were formed, the dichloromethane layer was separated from the aqueous layer, concentrated in vacuo, and added dropwise to methanol to precipitate the brominated polybutadiene. The yield of brominated phenyl terminated polybutadiene was 99 g (97 g in theory) after drying in vacuo at room temperature for 48 hours, and the product contained 64.4 wt% bromine (63.9 wt% in bromine). ). Some properties of the product are shown in Table 4.

Example 37

Phenyl terminated polybutadiene of 51 g (0.57 mol of unsaturated butenyl units, 0.36 mol of saturated butyl units and 0.03 mol of phenyl units) was used, and ˜3 mL of aqueous HBr (from scratch initially in the reaction flask prior to the start of bromine feed). 48% by weight), and brominated phenyl terminated partially hydrogenated polybutadiene was prepared as described in Example 36, except that neutralization was performed using sodium hydroxide. The product contained 66.8 wt% bromine (in theory, 63.9 wt% bromine). Some properties of this product are shown in Table 4.

Table 4

¹ brominated phenyl terminated partially hydrogenated polybutadiene, category vi).

Example 38 illustrates the synthesis of a mixture of tetrabromoxylene isomers belonging to flame retardant category iii).

Example  38

Xylene used in this preparation contained about 14% ethylbenzene. A 5 L three neck round bottom flask was equipped with a mechanical stirrer, Therm-o-Watch ^® thermometer, glycol cooled (0 ° C.) reflux condenser, addition funnel and ice cold corrosive scrubber. The flask was first charged with bromine (3196 g, 1031 mL, 20 mol) followed by dibromomethane (1500 mL) followed by iron powder (6 g, 325 mesh). The slurry was mechanically stirred at ambient temperature. The addition funnel was charged with xylene. Xylene was added to the stirred slurry over 2.25 hours. The reaction took place immediately and during the addition the reaction temperature rose from 30 ° C to 48 ° C. After the addition was complete, the reaction mixture was heated to reflux at 83 ° C. for a further 20 minutes. During this period, the reflux temperature rose to 91 ° C. After the reaction slurry was cooled to 25 ° C., water (1500 mL) was charged to the reactor to decompose the catalyst and steam distill the excess bromine and solvent. As the addition of water was exothermic, the temperature of the slurry rose to 45 ° C.

The equipment was set up for distillation and the slurry was heated to distill bromine and dibromomethane. Distillation started at 77 ° C. The bromine / dibromomethane distillate was collected while the aqueous phase continued to return to the reactor. A total of about 1200 mL of distillate was collected over 2 hours. After cooling the contents of the distillation vessel to ambient temperature, the slurry was filtered using a coarse sintered glass funnel. At this time, a sufficient amount of bromine still remained dissolved in solvent and water. Perhaps due to the strong affinity of the product for the solvent, distillation was stopped as the product and the residual solvent formed a relatively uniform mass (aggregate). The assembly was subjected to severe stress on the stirrer.

The crystalline solid on the filter frit was washed with water (2 × 500 mL) and then dried in air overnight, then in a forced convection oven at 92 ° C. for a light reddish solid weighing 1418.5 g. Obtained (Reap A). The filtrate was concentrated to about half of the original volume on a rotary evaporator and then cooled to room temperature. Thus an additional solid precipitate was obtained, which was separated by filtration and dried in air to give 19 g of a tan powdery solid (receipt B). Harvest A and Harvest B were combined and washed with acetone (2 × 2 L) to remove most of the color. Acetone was evaporated from the wash to give a near black solid weighed to 49.3 g. In gas chromatography-mass spectrometry (GC-MS) analysis, this material is mainly pentabromoethylbenzene (84.5 area%), and tetrabromoxylene (12.1 area%) and tetrabromo (methyl) benzyl bromide (12. 3.0 area%).

The washed mass was dried in air for 3 hours and then in an oven at 92 ° C. for 1 hour to yield 1524 g of an off-white solid, 90% yield as 3.6 moles of tetrabromoxylene. The melting point of tetrabromoxylene was 220 to 230 ° C. GC-MS of this product resulted in the following composition:

Tetrabromoxylene (3 isomers): 93.5 area%

Pentabromoethylbenzene: 6.5 area%

Example 39 illustrates the synthesis of brominated phenyl terminated poly (1,3-cyclohexadiene), which is a flame retardant of category viii).

Example 39

Phenyl terminated poly (1,3-cyclohexadiene) was prepared by coupling with a polymerization end with bromobenzene in a manner similar to the method described in Macromolecules , 1998, 31, 4687. Cyclohexane was passed through a short silica gel column to remove the polymerization inhibitor from the cyclohexane solvent. The glass vessel was oven dried and purged with nitrogen prior to use in the polymerization reaction. Cyclohexane, 1,3-cyclohexadiene, and bromobenzene were purged with nitrogen for about 30 minutes prior to use in the polymerization reaction. Cyclohexane (20 mL) was added via cannula to a fluid circulation jacketed four neck round bottom flask equipped with a mechanical overhead stirrer, thermocouple, rubber diaphragm, and nitrogen atmosphere. After the addition of the initiators N, N, N ', N'-tetramethylethylenediamine (TMEDA; 1.6 mL, 0.010 mol, 1.25 equiv) and n-BuLi (4.1 mL, 0.0083 mol), the mixture was heated for 50 minutes for about 10 minutes. Stir at ° C. The remaining cyclohexane (200 mL) was then added. To the mixture was rapidly added 1,3-cyclohexadiene (25.2 g, 0.314 mol) that had been de-stabilized and the resulting mixture was stirred at 50 ° C. for about 2 hours. Nitrogenated bromobenzene (6.5 g, 0.042 mol) was then added to terminate the polymer with a phenyl group. Isopropanol was added to precipitate the polymer. The precipitated polymer (phenyl terminated poly (1,3-cyclohexadiene)) was filtered and then rinsed with water, isopropanol, and methanol. The polymer obtained (26 g, M _n 3,000) was dried overnight at room temperature under reduced pressure.

Dry phenyl terminated poly (1,3-cyclohexadiene) (23.2 g, 0.278 mol reactive repeat unit) in a fluid circulating jacketed four neck round bottom flask with mechanical overhead stirrer, thermocouple, and nitrogen atmosphere To about 1 kg bromochloromethane and 56 g methanol. The ambient light source of the flask was minimized. The reaction temperature in the dropwise addition of bromine (14.3 mL, 44.6 g, 0.279 mol) ranged from 50 ° C. to 50 ° C. During bromine addition (after adding about 11 mL bromine) about 2 mL aqueous HBr was added. The bromination reaction process was monitored by ¹ H NMR (relative to the unsaturated group). The bromination reactant was removed by treating the reaction mixture with an aqueous solution containing 400 g of water, 2 g of sodium sulfite, and 7 g of sodium carbonate until the reaction mixture became basic (pH ˜9). Once two layers were formed, the bromochloromethane layer was separated from the aqueous layer and the bromochloromethane layer was concentrated in vacuo. The brominated polymer was dissolved in tetrahydrofuran and added dropwise to methanol to precipitate the brominated phenyl terminated polybutadiene. After drying for 48 hours in vacuo at room temperature, 43.6 g of a polymer containing 52.0 wt% (theoretical: 65.7 wt%) bromine were obtained.

Example  40-42

Examples 40-42 are brominated N, N'-1,3-phenylenebismaleimide, brominated N, N '-(4,4'-methylenediphenyl) bismaleimide, and N, N'-ethylenebis To illustrate the synthesis of flame retardants of maleimide, ie categories x), xi), and xii).

Example  40

This synthesis condition is not optimized. Chloroform (˜700 g) was placed in a fluid circulation jacketed four neck round bottom flask equipped with a mechanical overhead stirrer and thermocouple. 1,3-phenylenediimaleimide (20.2 g, 0.075 mol) was added to chloroform. Bromine (24.1 g, 0.151 mol) was added dropwise over ˜30 minutes to the dimaleimide solution under stirring at 50-55 ° C. The reaction was then stirred at 55 ° C overnight. Once a white precipitate formed, the reaction was cooled. The precipitate was filtered and then slurried, rinsed with aqueous sodium bicarbonate, and then washed with water and methanol. The solid was dried in an oven at 120 ° C. under reduced pressure to give 20 g of N, N′-1,3-phenylenebismaleimide in a yield of 45%. The brominated product was a yellow solid powder containing 53.1 wt% bromine (phase theory: 54.4 wt%).

Example  41

Dichloromethane (2.4 kg) was placed in a fluid circulation jacketed four neck round bottom flask equipped with a mechanical overhead stirrer and thermocouple. N, N '-(4,4'-methylenediphenylene) bismaleimide (502 g, 1.40 mol) was added to dichloromethane. Bromine (479 g, 2.82 mol) was added dropwise to the bismaleimide solution over 60 minutes under stirring. The initial circulation bath temperature was 43 ° C. After about 35 mL bromine was added, an exothermic precipitation began. After slowing down the bromine addition rate, the bath temperature was lowered to 30 ° C. to control the reaction temperature (<41 ° C.). After the bromine addition was complete, the reaction mixture was heated at 43 ° C overnight. The volume of dichloromethane and residual bromine were reduced by distillation with a basic scrubber (10 wt% sodium carbonate, 10 wt% sodium sulfite). Methanol (~ 1 kg) was added to slurry the precipitated solid, then the slurry was filtered, the precipitate was rinsed three times with methanol and then dried in an oven under reduced pressure to yield N, N'1- (4s4'-methylenediphenylene). 843 g of bismaleimide were obtained with a yield of 89%. The brominated product was an off-white solid powder containing about 47.1 wt% bromine.

Example  42

Dichloromethane (˜100 g) was placed in a flow-circulating jacketed four neck round bottom flask equipped with a mechanical overhead stirrer and thermocouple. Ethylenediamine bismaleimide (22.9 g, 0.104 mol) was added to dichloromethane. Bromine (33.2 g, 0.208 mol) was added dropwise to the bismaleimide solution under reflux stirring. A precipitate began to form after about 3.5 hours and the reaction mixture was stirred overnight. The volume of dichloromethane and residual bromine were reduced by distillation with a basic scrubber (10 wt% sodium carbonate, 10 wt% sodium sulfite). After adding methanol (˜100 g) to slurry the precipitated solid, the slurry was filtered, the precipitate was rinsed with methanol and water and dried under reduced pressure in an oven at 100 ° C. to obtain 39 g of brominated N, N′-ethylenebismaleimide. Yield 69.5%. This brominated product was an off-white solid powder containing about 59.2 wt% bromine.

Example 43 illustrates the synthesis of novolak brominated allyl ether, ie flame retardants of category vii). In Example 43, all equivalents were based on novolaks.

Example 43 9016-27 (XP-7203)

Allyl alcohol (138 g, 2.4 mol, 10 equiv), dimethylcarbonate (214 g, 2.4 mol, 10 equiv), and catalytic amount of sodium methoxide (0.4 g, 7.1 mmol, 0.03 equiv) were added to the mechanical overhead stirrer, It was added to a 500 mL fluid circulation jacketed four necked round bottom flask equipped with a thermocouple and a nitrogen atmosphere and then stirred at 24 ° C. for 30 minutes. Phenol-formaldehyde novolak (25 g, 0.24 mol, M _w ~ 1135 g / mol, ~ 105 g / equivalent hydroxyl, DURITE ^® SD-1731, Borden Chemical, Inc., Louisville, KY) was catalyzed by triphenyl Phosphine (0.1 g, 0.4 mmol, 0.15 equiv) and 5% palladium on carbon (0.3 g) were added to the reaction mixture. The reaction was heated to about 81 ° C (circulation bath heated to 87 ° C). The reaction process was monitored by ¹ H NMR spectroscopy and completed after about 5 hours. The reaction mixture was washed with aqueous sodium carbonate and then the organic phase was filtered through Celite ^® . After the solvent was removed, the product novolak allyl ether was dried at about 40 ° C. under vacuum for about 24 hours.

About 1 kg of dichloromethane and about 30 g of novolak allyl ether in methanol (62 g, 5.5% by weight) in a 2 L fluid circulation jacketed 5-neck round bottom flask with mechanical overhead stirrer, thermocouple, and nitrogen atmosphere (0.11 mol) was added. Bromine (34 g, 0.22 mol, 2 equiv) was added dropwise to the solution over 15 minutes at 15 ° C. under a nitrogen atmosphere. The reaction mixture was raised to 28 ° C. over 1 hour. About 3 mL (48 wt.%) Of aqueous HBr was slowly added to the reaction mixture over 3 hours. The reaction was monitored by ¹ H NMR spectroscopy and completed after 3.25 hours. The reaction mixture was washed with aqueous sodium carbonate and aqueous sodium sulfite. Brominated product by separating the dichloromethane layer, reducing the solvent volume of the dichloromethane solution, and then dropping the dichloromethane solution into methanol to form a dilute solution of dichloromethane (about 10% by weight) in methanol. Precipitated. The precipitated product was dried under vacuum at room temperature for 48 hours to give brominated allyl ether of phenol-formaldehyde novolak containing 51.1 wt% bromine (phase theory: 53.0 wt%).

Represented in the singular or in the plural, reactants or components represented by chemical names or chemical formulas throughout the text are meant to exist before contact with another substance (eg, another reactant, solvent, etc.) represented by the chemical name or chemical type. Should be considered. It is not important what chemical changes, modifications and / or reactions have occurred beforehand in the mixture or solution or reaction medium obtained, which reactants are specific under the conditions under which such changes, modifications and / or reactions are required in accordance with the present disclosure. And / or the natural result of associating the components. Thus, the reactants and components mean those elements associated with carrying out the desired chemical operation or reaction or with forming a mixture to be used to carry out the desired operation or reaction. Also in the embodiments where a substance, ingredient and / or element is mentioned under the present tense (including, including, "comprising", "comprising", "is", etc.), it is one or more other in accordance with the present disclosure. By material, component or element is meant the same substance, component or element as it is just before being first contacted, blended or mixed with the substance, element and / or element.

In addition, even when a substance is referred to under the present tense (eg, “comprises”, “comprises”, etc.) in the claims, it is present just before being first contacted, blended, or mixed with one or more other substances in accordance with the present disclosure. It means the same material as that. All patents and publications mentioned in any part of this specification are incorporated by reference in their entirety into this disclosure as if set forth in their entirety herein.

Except as otherwise specifically indicated, the singular expressions as used herein are not intended to be limited to the description or the single element to which the singulars are applied, and should not be considered as limiting. Rather, the singular forms as used herein are intended to include one or more such elements unless specifically stated otherwise in the text.

The invention can vary quite broadly within the spirit and scope of the appended claims. Accordingly, the above description is not intended to be exhaustive or to limit the invention to the specific embodiments presented above.

Claims (68)

A flame retardant styrenic polymer foam composition comprising a styrenic polymer and a flame retardant amount of a flame retardant, obtained by including in the foam recipe before or during foam formation: i) at least one dieter of tetrabromobisphenol-S, wherein the ether group does not contain bromine and at least one of the ether groups is an allyl group; or ii) at least one dieter of tetrabromobisphenol-S, wherein at least one of the ether groups contains bromine; or iii) at least one substituted benzene having a total of six substituents on the ring, wherein at least three of the substituents are bromine atoms and at least two of the substituents are C _1-4 alkyl groups; or iv) tribromoneopentyl alcohol; or v) at least one tris (dibromoalkyl) benzenetricarboxylate each dibromoalkyl group independently containing 3 to 8 carbon atoms; or vi) at least one partially hydrogenated, aryl terminated, or partially hydrogenated and aryl terminated brominated polybutadiene; or vii) at least one brominated allyl ether of novolak; or viii) at least one brominated aryl terminated poly (1,3-cycloalkadiene); or ix) at least one brominated poly (4-vinylphenol allyl ether); or x) at least one brominated N, N'-phenylenebismaleimide; or xi) at least one brominated N, N '-(4,4'-methylenediphenyl) bismaleimide; or xii) at least one brominated N, N'-ethylenebismaleimide; or xiii) ethylenebis (dibromonobonan-dicarboximide); or xiv) tetrabromobisphenol-A; or xv) a combination of any two or more of i) to xiv). 2. A flame retardant styrenic polymer foam composition according to claim 1, wherein the styrenic polymer foam composition is in the form of a) expandable styrene-based polymer beads or granules or b) in the form of an extruded styrene-based polymer foam; When the styrene-based polymer foam composition is a), the flame retardant is as follows:  i) at least one dieter of tetrabromobisphenol-S, wherein the ether group does not contain bromine and at least one of the ether groups is an allyl group; or ii) at least one dieter of tetrabromobisphenol-S, wherein at least one of the ether groups contains bromine; or iii) at least one substituted benzene having a total of six substituents on the ring, wherein at least three of the substituents are bromine atoms and at least two of the substituents are C _1-4 alkyl groups; or iv) tribromoneopentyl alcohol; or v) at least one tris (dibromoalkyl) benzenetricarboxylate each dibromoalkyl group independently containing 3 to 8 carbon atoms; or vi) at least one partially hydrogenated, aryl terminated, or partially hydrogenated and aryl terminated brominated polybutadiene; or vii) at least one brominated allyl ether of novolak; or A combination of any two or more of i) to vii) above; When the styrene-based polymer foam composition is b), the flame retardant is a composition as follows: ii) at least one dieter of tetrabromobisphenol-S, wherein at least one of the ether groups contains bromine; or iii) a substituted benzene having a total of 6 substituents on the ring above, wherein not less than three of the substituents are bromine atoms, two of the substituents are one or more C _{1 -4} alkyl group; or iv) tribromoneopentyl alcohol; or v) at least one tris (dibromoalkyl) benzenetricarboxylate each dibromoalkyl group independently containing 3 to 8 carbon atoms; or vi) at least one partially hydrogenated, aryl terminated, or partially hydrogenated and aryl terminated brominated polybutadiene; or vii) at least one brominated allyl ether of novolak; or viii) at least one brominated poly (1,3-cycloalkadiene); or ix) at least one brominated poly (4-vinylphenol allyl ether); or x) at least one brominated N, N'-phenylenebismaleimide; or xi) at least one brominated N, N '-(4,4'-methylenediphenyl) bismaleimide; or xii) at least one brominated N, N'-ethylenebismaleimide; or xiii) ethylenebis (dibromonobonan-dicarboximide); or xiv) tetrabromobisphenol-A; or A combination of any two or more of ii) to xiv) above. The composition of claim 2, wherein no other flame retardant is used. 4. The composition of claim 3, wherein said styrenic polymer foam composition is in the form of expandable styrenic polymer beads or granules, wherein said composition comprises at least one synergist or at least one heat stabilizer. 4. The composition of claim 3, wherein said styrenic polymer foam composition is in the form of an extruded styrenic polymer foam and wherein said composition comprises one or more synergists or one or more heat stabilizers. The flame retardant according to claim 1, wherein the flame retardant is at least one tetrabromobisphenol-S diester, the ether group does not contain bromine, at least one of the ether groups is an allyl group, and the tetrabromobisphenol-S The dieter of which is bis (allyl ether) of tetrabromobisphenol-S. The flame retardant according to claim 1, wherein the flame retardant is at least one tetrabromobisphenol-S dieter, at least one of the ether groups contains bromine, and the dieter of tetrabromobisphenol-S is tetrabromobis The composition is bis (2,3-dibromopropyl ether) of phenol-S. The method of claim 1, wherein the flame retardant is a bromine atom is more than two of the substituents is two or more of the substituents C _{1 -4} alkyl group, tetra on the ring one or more as at least one substituted benzene having a total of 6-bromo substituent The composition is moylene. The composition of claim 1 wherein said flame retardant is tribromoneopentyl alcohol. The flame retardant according to claim 1, wherein the flame retardant is at least one tris (dibromoalkyl) benzenetricarboxylate each dibromoalkyl group independently containing 3 to 8 carbon atoms, and the tris (dibromoalkyl) benzenetricarboxylate The composition is tris (2,3-dibromopropyl) 1,2,4-benzenetricarboxylate or tris (2,3-dibromopropyl) 1,3,5-benzenetricarboxylate. The composition of claim 1 wherein said flame retardant is at least one brominated aryl terminated partially hydrogenated polybutadiene. The composition of claim 1 wherein the flame retardant is at least one novolak brominated allyl ether. The method of claim 1, wherein the flame retardant is at least one brominated poly (1,3-cycloalkadiene) and the brominated poly (1,3-cycloalkadiene) is at least one brominated poly (1,3-cyclohexa Dienes) or one or more brominated aryl terminated poly (1,3-cyclohexadienes). The composition of claim 1 wherein the flame retardant is one or more brominated poly (4-vinylphenol allyl ether). The composition of claim 1, wherein said flame retardant is one or more brominated N, N'-phenylenebismaleimide. The composition of claim 1 wherein said flame retardant is at least one brominated N, N '-(4,4'-methylenediphenyl) bismaleimide. The composition of claim 1 wherein said flame retardant is at least one brominated N, N'-ethylenebismaleimide. A composition according to claim 1, wherein the flame retardant is ethylenebis (dibromonobonane-dicarboximide). The composition of claim 1 wherein the flame retardant is tetrabromobisphenol-A. 3. The composition of claim 2, wherein said styrenic polymer foam composition is in the form of expandable styrenic polymer beads or granules. 21. The composition of claim 20, wherein said styrenic polymer of said expandable styrenic beads or granules comprises, on average, at least 80% by weight of styrene polymer. 3. The composition of claim 2, wherein said styrenic polymer foam composition is in the form of an extruded styrenic polymer foam. 23. The composition of claim 22, wherein said extruded styrenic polymer foam comprises at least 80% by weight of styrene polymer. The composition of claim 1, wherein said styrenic polymer is crystalline polystyrene. 5. The composition of claim 4, wherein a synergist is included and said synergist is dicumyl. 26. The method of claim 25, wherein the flame retardant is a bromine atom is more than two of the substituents is two or more of the substituents C _{1 -4} alkyl group, tetra on the ring one or more as at least one substituted benzene having a total of 6-bromo substituent The composition is moylene. 6. The composition of claim 5, wherein a synergist is included and said synergist is dicumyl. The method of claim 27, wherein the flame retardant is a bromine atom is more than two of the substituents is two or more of the substituents C _{1 -4} alkyl group, tetra on the ring one or more as at least one substituted benzene having a total of 6-bromo substituent The composition is moylene. The composition of claim 27 wherein said flame retardant is tetrabromobisphenol-A. 5. The composition of claim 4, wherein a heat stabilizer is included and said heat stabilizer is dibutyl tin maleate or hydrocalcite. 31. The composition of claim 30, wherein said heat stabilizer is dibutyl tin maleate and said flame retardant is at least one brominated aryl terminated partially hydrogenated polybutadiene. 6. The composition of claim 5, wherein a heat stabilizer is included and said heat stabilizer is dibutyl tin maleate or hydrocalcite. 31. The method of claim 30 wherein the heat stabilizer is dibutyl tin maleate and the flame retardant is at least one brominated aryl terminated partially hydrogenated polybutadiene or at least one brominated aryl terminated poly (1,3-cycloalkadiene) Phosphorus composition. A process for preparing a flame retardant styrenic polymer foam composition according to claim 1, comprising the following in the foam recipe of said composition before or during foam formation: i) at least one dieter of tetrabromobisphenol-S, wherein the ether group does not contain bromine and at least one of the ether groups is an allyl group; or ii) at least one dieter of tetrabromobisphenol-S, wherein at least one of the ether groups contains bromine; or iii) at least one substituted benzene having a total of six substituents on the ring, wherein at least three of the substituents are bromine atoms and at least two of the substituents are C _1-4 alkyl groups; or iv) tribromoneopentyl alcohol; or v) at least one tris (dibromoalkyl) benzenetricarboxylate each dibromoalkyl group independently containing 3 to 8 carbon atoms; or vi) at least one partially hydrogenated, aryl terminated, or partially hydrogenated and aryl terminated brominated polybutadiene; or vii) at least one brominated allyl ether of novolak; or viii) at least one brominated poly (1,3-cycloalkadiene); or ix) at least one brominated poly (4-vinylphenol allyl ether); or x) at least one brominated N, N'-phenylenebismaleimide; or xi) at least one brominated N, N '-(4,4'-methylenediphenyl) bismaleimide; or xii) at least one brominated N, N'-ethylenebismaleimide; or xiii) ethylenebis (dibromonobonan-dicarboximide); or xiv) tetrabromobisphenol-A; or xv) a combination of any two or more of i) to xiv). A process for preparing expandable styrenic beads or granules from a suspension-polymerizable mixture consisting of one or more styrenic monomers, comprising the flame retardant amount of the flame retardant of claim 34 in the mixture. 36. The method of claim 35, wherein said at least one styrene monomer is a mixture of styrene monomers and at least 80% by weight of said monomer is styrene. 36. The method of claim 35, wherein said at least one styrenic monomer is styrene. A method of making large expandable beads or granules of one or more styrenic polymers, the method comprising expanding small beads or granules formed from a suspension polymerization recipe comprising at least one flame retardant of claim 34. 39. The method of claim 38, wherein said small styrenic beads or granules and said large styrenic beads or granules are at least 80% by weight of styrene. 39. The method of claim 38, wherein said small styrenic beads or granules and said large styrenic beads or granules are made of styrene. A method of making a styrenic polymer foam, the method comprising molding expanded beads or granules of at least one styrenic polymer formed from the recipe comprising at least one flame retardant of claim 34. 42. The method of claim 41, wherein said at least one styrenic polymer consists of at least 80 wt% styrene. 42. The method of claim 41 wherein said at least one styrenic polymer is styrene. A process for producing an extruded styrenic foam from a foamable melted styrenic polymer mixture, the method comprising the flame retardant of claim 34 in the mixture. 45. The method of claim 44, wherein said styrenic polymer consists of at least 80 wt% styrene polymer. 45. The method of claim 44, wherein said styrenic polymer is crystalline polystyrene. A flame retardant styrenic polymer foam recipe comprising a flame retardant amount of a flame retardant, wherein the recipe is as follows before at least the flame retardant is included: i) at least one dieter of tetrabromobisphenol-S, wherein the ether group does not contain bromine and at least one of the ether groups is an allyl group; or ii) at least one dieter of tetrabromobisphenol-S, wherein at least one of the ether groups contains bromine; or iii) a substituted benzene having a total of 6 substituents on the ring above, wherein not less than three of the substituents are bromine atoms, two of the substituents are one or more C _{1 -4} alkyl group; or iv) tribromoneopentyl alcohol; or v) at least one tris (dibromoalkyl) benzenetricarboxylate each dibromoalkyl group independently containing 3 to 8 carbon atoms; or vi) at least one partially hydrogenated, aryl terminated, or partially hydrogenated and aryl terminated brominated polybutadiene; or vii) at least one brominated allyl ether of novolak; or viii) at least one brominated poly (1,3-cycloalkadiene); or ix) at least one brominated poly (4-vinylphenol allyl ether); or x) at least one brominated N, N'-phenylenebismaleimide; or xi) at least one brominated N, N '-(4,4'-methylenediphenyl) bismaleimide; or xii) at least one brominated N, N'-ethylenebismaleimide; or xiii) ethylenebis (dibromonobonan-dicarboximide); or xiv) tetrabromobisphenol-A; or xv) a combination of any two or more of i) to xiv). 48. The flame retardant of claim 47, wherein at least the flame retardant prior to inclusion in the recipe is at least one diester of tetrabromobisphenol-S, the ether group does not contain bromine, and at least one of the ether groups is an allyl group The styrenic polymer foam recipe in which the said diether of tetrabromobisphenol-S is bis (allyl ether) of tetrabromobisphenol-S. 48. The method of claim 47, wherein at least the flame retardant prior to inclusion in the recipe is at least one diester of tetrabromobisphenol-S, at least one of the ether groups contains bromine and the tetrabromobisphenol-S A styrenic polymer foam recipe wherein the diether of is bis (2,3-dibromopropyl ether) of tetrabromobisphenol-S. The method of claim 47, wherein at least one having at least a transfer of the flame retardant is included in the recipe of 6 substituents on the 3 and above the bromine atom is more than 2 of the substituents is two C _{1 -4} alkyl group, a ring of the substituent A styrenic polymer foam recipe, wherein the substituted benzene is at least one tetrabromoxylene. 48. The styrenic polymer foam recipe of claim 47, wherein at least the flame retardant prior to inclusion in the recipe is tribromoneopentyl alcohol. 48. The flame retardant of claim 47 wherein at least the flame retardant prior to inclusion in the recipe is at least one tris (dibromoalkyl) benzenetricarboxylate wherein each dibromoalkyl group independently contains 3 to 8 carbon atoms, Dibromoalkyl) benzenetricarboxylate is tris (2,3-dibromopropyl) 1,2,4-benzenetricarboxylate or tris (2,3-dibromopropyl) 1,3,5-benzenetricarboxylate Phosphorus Styrenic Polymer Foam Recipe. 48. The styrenic polymer foam recipe of claim 47, wherein said flame retardant at least prior to inclusion in said recipe is at least one brominated aryl terminated partially hydrogenated polybutadiene. 48. The styrenic polymer foam recipe of claim 47, wherein said flame retardant at least prior to inclusion in said recipe is at least one novolak brominated allyl ether. 48. The brominated poly (1,3-cycloalkadiene) of claim 47, wherein said flame retardant at least prior to inclusion in said recipe is at least one brominated poly (1,3-cycloalkadiene) and said brominated poly (1,3-cycloalkadiene) is at least one brominated. A styrenic polymer foam recipe that is poly (1,3-cyclohexadiene) or one or more brominated aryl terminated poly (1,3-cyclohexadiene). 48. The styrenic polymer foam recipe of claim 47, wherein the flame retardant at least prior to inclusion in the recipe is at least one brominated poly (4-vinylphenol allyl ether). 48. The styrenic polymer foam recipe of claim 47, wherein at least the flame retardant prior to inclusion in the recipe is at least one brominated N, N'-phenylenebismaleimide. 48. The styrenic polymer foam recipe of claim 47, wherein at least the flame retardant prior to inclusion in the recipe is at least one brominated N, N '-(4,4'-methylenediphenyl) bismaleimide. 48. The styrenic polymer foam recipe of claim 47, wherein said flame retardant at least prior to inclusion in said recipe is at least one brominated N, N'-ethylenebismaleimide. 48. The styrene-based polymer foam recipe of claim 47, wherein at least the flame retardant prior to inclusion in the recipe is ethylenebis (dibromonobonan-dicarboximide). 48. The styrenic polymer foam recipe of claim 47, wherein said flame retardant at least prior to inclusion in said recipe is tetrabromobisphenol-A. A material composition comprising one or more of the following: a) brominated partially hydrogenated polybutadiene; b) brominated aryl terminated polybutadiene; c) brominated aryl terminated partially hydrogenated polybutadiene; d) brominated allyl ether of novolak; e) brominated poly (1,3-cycloalkadiene); f) brominated aryl terminated poly (1,3-cyclohexadiene); g) brominated N, N'-phenylenebismaleimide; h) brominated N, N'-1,3-phenylenebismaleimide; i) brominated N, N '-(4,4'-methylenediphenyl) bismaleimide; or j) brominated N, N'-ethylenebismaleimide. 63. A process for the preparation of brominated aryl terminated partially hydrogenated polybutadienes according to claim 62, wherein bromine and one or more aryl terminated partially hydrogenated polybutadienes are contacted in a liquid medium to form brominated aryl terminated partially hydrogenated polybutadienes. Method comprising forming. 63. A process for the preparation of novolak brominated allyl ether according to claim 62 comprising contacting bromine with at least one novolak brominated allyl ether in a liquid medium. 63. A process for preparing the brominated poly (1,3-cycloalkadiene) according to claim 62, comprising contacting bromine with at least one poly (1,3-cycloalkadiene) in a liquid medium. 63. A process for the preparation of brominated N, N'-phenylenebismaleimide according to claim 62, comprising contacting bromine with at least one N, N'-phenylenebismaleimide in a liquid medium. 63. A method for producing the brominated N, N '-(4,4'-methylenediphenyl) bismaleimide according to claim 62, wherein bromine and N, N'-(4,4'-methylenediphenyl) bismaleimide Contacting in a liquid medium. 63. A process for the preparation of brominated N, N'-ethylenebismaleimide according to claim 62, comprising contacting bromine with N, N'-ethylenebismaleimide in a liquid medium.